Combatting pests with o-pyrazolo-pyrimidine-(thiono)-phosphoric(phosphonic)acid esters

ABSTRACT

1. A METHOD OF COMBATING A PEST SELECTED FROM THE GROUP CONSISTING OF INSECT, ACARID, AND NEMATODE PEST WHICH COMPRISES APPLYING TO THE PESTS OR A HABITAT THEREOF AN INSECTICIDALLY, ACARICIDALLY, OR NEMATOCIDALLY EFFECTIVE AMOUNT OF AN O-PYRAZOLOPYRIMIDINE-(THIONO)-PHOSPHORIC (PHOSPHONIC) ACID ESTER OF THE FORMULA:   2-(R1-O-P(=X)(-R2)-O-),3-R3,7-(H3C-)-PYRAZOLO(1,5-A)-   PYRIMIDINE   IN WHICH R1 IS ALKYL WITH 1 TO 6 CARBON ATOMS, R2 IS ALKYL WITH 1 TO 4 CARBON ATOMS OR ALKOXY WITH 1 TO 6 CARBON ATOMS, R3 IS HYDROGEN, CHLORINE OR BROMINE, AND X IS OXYGEN OR SULFUR.

United States Patent 6 US. Cl. 424-200 10 Claims ABSTRACT OF THE DISCLOSURE O-pyrazolo-pyrimidine-(thiono)-phosphric (phosphonic) acid esters of the general formula P-O R3 R2 N nae-U in which R is an alkyl radical with 1 to 6 carbon atoms,

R is an alkyl radical with 1 to 4 carbon atoms or an alkoxy radical with 1 to 6 carbon atoms,

R is hydrogen, chlorine or bromine, and

X is oxygen or sulfur,

which possess insecticidal, acaricidal, nematocidal, fungicidal and molluscicidal properties.

This is a division, of application Ser. No. 158,046 filed June 29, 1971, now US. Pat. No. 3,761,479.

The present invention relates to and has for its object the provision of new O-pyrazolo-pyrimidine-(thiono)- phosphoric (phosphonic) acid esters, i.e. 2-hydroxy-3- optionally chloroor bromo-substituted-7-methyl-pyrazolo(l,5-a) pyrimidine esters of (thiono)-phosphoric (alkane-phosphonic) acid esters, which possess insecticidal, acaricidal, nematocidal, fungicidal and molluscicidal properties, active compositions in the form of mixtures of such compounds with solid and liquid dispersible carrier vehicles, and methods for producing such compounds and for using such compounds in a new way especially for Combating pests, e.g. insects, acarids, nematodes, fungi and molluscs, especially insects, acarids and nematodes, with other and further objects becoming apparent from a study of the within specification and accompanying examples.

It is known from Belgian Patent Specification 676,802 and published Dutch Patent Application 65/16,907 that O-pyrazolopyrimidine (thiono)-phosphoric(phosphonic, phosphinic) acid ester derivatives, for example 0,0-di ethyl-O-[5,7 dimethylpyrazolo(1,5-a)-pyrimidine- (2)y1]- phosphoric acid ester, exhibit pesticidal activity, particularly insecticidal and acaricidal activity.

The present invention provides O-pyrazolopyrimidine- Patented Oct. 29, 1974 (thiono)-phosphoric(phosphonic) acid esters of the general formula:

R is an alkyl radical with 1 to 6 carbon atoms,

R is an alkyl radical with 1 to 4 carbon atoms or an alkoxy radical with 1 to 6 carbon atoms,

R is hydrogen, chlorine or bromine, and

X is oxygen or sulfur.

in which These compounds have been found to possess strong insecticidal, acaricidal (including tickicidal) and nematocidal properties.

The invention also provides a process for the production of an O-pyrazolo-pyrimidine-(thiono)-phosphoric (phosphonic) acid ester derivative of formula (I) in which a (thiono)phosphoric(phosphonic) acid ester halide of the. general formula:

P-Hal in which R R and X have the meanings stated above, and Hal is halogen, preferably chlorine,

is reacted with a 2-hydroxypyrazolopyrimidine derivative of the general formula:

R has the meaning stated above,

in which 0 the art.

If O-ethylethanephosphonic acid ester chloride and 2- hydroxy-7-methyl-pyrazolo(1,5-a)-pyrimidine are used as starting materials, the reaction course can be represented by the following formula scheme:

Preferably, R is a straight or branched alkyl radical of l to 4 carbon atoms, and may for example be a methyl, ethyl, nor iso-propyl, or n-, sec.-, tert.- or iso-butyl radical; and R is a methyl, ethyl, methoxy, ethoxy, nor iso-propyl, or n-butoxy, sec.-butoxy or tert.-butoxy radical.

As examples of (thiono)phosphoric(phosphonic) acid ester halides of formula (II) which can be used in the process, there are mentioned in particular: 0,0-dimethyl-, 0,0-diethy1-, 0,0-dipropyl-, 0,0-di-iso-propyl-, 0,0-dibutyl-, 0,0-di-tert.-butyl-, O-methyl-O-ethyl-, O-methyl- O-iso-propyl-, O-methyl-O-butyl-, O-ethyl-O-iso-propyl-, O-ethyl-O-butylphosphoric acid ester chlorides or bromides and their thiono analogues; and O-methyl-methane-, O-methyl-ethane-, O-ethyl-methane-, O-propylmethane-, O propyl-ethane, O iso-propyl-methane-, O iso-propyl ethane-, O-butyl-methane-, O-butyl-ethane-, O-tert.-butylmethanephosphonic acid ester chlorides or bromides and their thiono analogues.

The (thiono)phosphoric(phosphonic) acid ester halides to be used as starting materials are known and can be prepared according to customary processes. The 2-hydroxypyrazolopyrimidines of the formula (III) may be obtained from 3-aminopyrazolone and acetoacetaldehydedimethylacetal and, if appropriate, halogenation in 3 position.

The reaction of the invention is preferably carried out in the presence of a solvent, which term includes a mere diluent. As such, practically all inert organic solvents are suitable. These include especially aliphatic and aromatic optionally chlorinated hydrocarbons, such as benzene, toluene, xylene, benzine, methylene chloride, chloroform, carbon tetrachloride and chlorobenzene; ethers, such as diethyl ether, dibutyl ether and dioxane; ketones, such as acetone, methylethyl ketone, methylisopropyl ketone and methylisobutyl ketone; and in particular nitriles, such as acetonitrile.

As acid acceptors, all customary acid-binding agents can be used. Particuarly good results have been obtained with alkali metal carbonates and alcoholates, such as sodium or potassium carbonate, methylate or ethylate; aliphatic, aromatic or heterocyclic amines, for example triethylamine, dimethylamine, dimethylaniline, dimethylbenzylamine and pyridine.

The reaction temperature can be varied within a fairly wide range. In general the reaction is carried out at about 0 to 100 C., preferably at about 15 to 35 C.

The reaction is, in general, carried out at normal pressure.

In carrying out of the process, the starting materials are generally used in equimolar proportions. An excess of one or the other of the reaction components seems to bring no substantial advantages. The reaction is preferably carried out in the presence of one of the above-mentioned solvents, and in the presence of an acid acceptor, at the temperatures stated; after several hours stirring, the reaction mixture is worked up as usual.

The substances according to the invention are obtained in most cases in the form of colorless to slightly yellowcolored viscous, water-insoluble oils which cannot be distilled without decomposition but which can, by'so- Called slight distillation (that is, by longer heating to moderately elevated temperatures under reduced pressure), be freed from the last volatile components and in this way be purified. The refractive index is particularly useful for their characterization. Those compounds which are crystalline may be characterized by their melting point.

As already mentioned, the new O-pyrazolopyrimidine- (thiono)-phosphoric(phosphonic) acid esters are distinguished by an outstanding insecticidal and acaricidal elTectiveness against plant pests, hygiene pests and pests of stored products and animal parasites. They possess a good activity against both sucking and biting insects, including blowfiies, and mites (acarina), including parasitic ticks. At the same time they exhibit a low phytotoxicity. In addition, some of the compounds have also a fungicidal, mol luscicidal and nematocidal activity.

For these reasons, the products according to the invention may be used with success as pesticides in crop protection and the protection of stored products as well as in the hygiene field.

To the sucking insects contemplated herein there belong, in the main, aphids (Aplzidae) such as the green peach aphid (Myzus persicae), the bean aphid (Dorah's fabae), the bird cherry aphid (Rlzopalosiphum padi), the pea aphid (Macrosiplmnz pisi) and the potato aphid (Laplzygma frngipcrlla) and coton worm (Prodelzia coclzleariae), the blossom beetle (Mcligethes aeneus), mali), the mealy plum aphid (Hyalopterus arlmdinis) and the cherry black-fly (Myzus cerasi); in addition, scales and mealybugs (Coccina), for example the oleander scale (Aspidiotus hederae) and the soft scale (Lecam'um hesperidum) as well as the grape mealybug (Pseudococcus marilimus); thrips (T/zysanoptern), such as Hercinorhri s felnoralis, and bugs, for example the beet bug (Piesma quadrara), the red cotton bug (Dysdercus intermedius), the bed bug (Cimex lcctularius), the assassin bug (Rhoa'nius prolixus) and Chagas bug (T riatoma infesmns) and, further, cicadas, such as Euscelis bilobatus and Nephotettix bipuncmlus; and the like.

In the case of the biting insects contemplated herein, above all there should be mentioned butterfly caterpillars (Lepidoptcra) such as the diamond-back moth (Plutella maculipelmis), the gypsy moth (Lymantrz'a dispar), the brown-tail moth (Euprocris chrysorrhoea) and tent caterpillar (Malacosoma neustria); further, the cabbage moth (Mamestra brassicae) and the cutworm (Agrotis segelum), the large white butterfly (Pieris brassicae), the small winter moth (Cheimatobia brumata), the green oak tortrix moth (T ortrix viridana), the fall armyworm (Laphygma frugiperda) and cotton Worm (prodenia Iitura), the ermine moth (Hyponomeuta padella), the Mediterranean flour moth (Eplzestia kt'ihnieI/a) and greater wax moth (Galleria mellonella); and the like.

Also to be classed with the biting insects contemplated herein are beetles (Coleoptera), for example the granary weevil (Sitophilus granarius-Calandra granaria), the Colorado beetle (Leptinotarsa decemlineata), the dock beetle (Gastroplzysa viridula), the mustard beetle (Phaedon cochlearine, the blossom beetle (MeIiger/zes aeneus), the raspberry beetle (Byturus tomenzosus), the bean weevil (Bruchz'dius-Acanthoscelides obleclus), the leather beetle (Dernmrtes frisclzi), the khapra beetle (Trogoderma granarz'unl), the flour beetle (Triboliunz CGJIHIIEIUTZ), the northern corn billbug (Calandra or Sitophilus zeamais), the drugstore beetle (Stegobium paniceum), the yellow mealworm (Tenebrio nzohtor) and the saw-toothed grain beetle (OryZaep/Il'lus surinamcnsis), and also species living in the soil, for example wireworms (Ag/"fates spec.)

and larvae of the cockchafer (Melolontha melolonrlza); cockroaches, such as the German cockroach (Blaltella germanica), American cockroach (Periplaneta antericana), Madeira cockroach (Leucophaea or Rhyparobia maderae), Oriental cockroach (Blatta orientalis), the giant cockroach (Blaberus giganteus) and the black giant cockroach (Blaberus fuscus) as Well as Hensclzoutedenia flexivitta; further, Orthoptera, for example the house cricket (Acheta domesticus); termites such as the eastern subterranean termite (Reticulitermes flavipes) and Hymenoptera such as ants, for example the garden ant (Lasius niger); and the like.

The Diptera contemplated herein comprise essentially the flies, such as the vinegar fly (Drosoplrila melanogaster), the Mediterranean fruit fly (Ceratitis Capilata), the house fly (Musca domestica), the little house fly (Fannia canicularis), the black blow fiy (Phormia regina) and bluebottle fiy (Calliphora erythrocephala) as well as the stable fly (Stomoxys calcitraizs); further gnats, for example mosquitoes such as the yellow fever mosquito (Aedes aegypli), the northern house mosquito (Culex pipiens) and the malaria mosquito (Anopheles stephensi); and the like.

With the mites (Acaria) contemplated herein there are classed, in particular, the spider mites (Tetranychidae) such as the two-spotted spider mite (Tetranychus telarius =Tetranychus althaeae or Tetranychus urticae) and the European red mite (Paratetranychus pil0sus=Pan0nyclius ulmi), gall mites, for example the black currant gall mite (Eriophyes ribis) and tarsonemids, for example, the broad mite (Hemitarsonemus latus) and the cyclamen mite (Tarsonemus pallidus); finally, ticks, such as the relapsing fever tick (Ornithoderus moubata); and the like.

When applied against hygiene pests and pests of stored products, particularly flies and mosquitoes, the process products are also distinguished by an outstanding residual activity on wood and clay, as well as a good stability to alkali on limed substrates.

The active compounds according to the instant invention can be utilized, if desired, in the form of the usual formulations or compositions with conventional inert (i.e. plant compatible or herbicidally inert) pesticide diluents or extenders, i.e. diluents, carriers or extenders of the type usable in conventional pesticide formulations or compositions, e.g. conventional pesticide dispersible carrier vehicles such as gases, solutions, emulsions, suspensions, emulsifiable concentrates, spray powders, pastes, soluble powders, dusting agents, granules, etc. These are prepared in known manner, for instance by extending the active compounds with conventional pesticide dispersible liquid diluent carriers and/or dispersible solid carriers optionally with the use of carrier vehicle assistants, e.g. conventional pesticide surface-active agents, including emulsifying agents and/or dispersing agents, whereby, for example, in the case where water is used as diluent, organic solvents may be added as auxiliary solvents. The following may be chiefly considered for use as conventional carrier vehicles for this purpose: aerosol propellants which are gaseous at normal temperatures and pressures, such as Freon; inert dispersible liquid diluent carriers, including inert organic solvents, such as aromatic hydrocarbons (e.g. benzene, toluene, xylene, etc.), halogenated, especially chlorinated, aromatic hydrocarbons (e.g. chlorobenzenes, etc.), paraffins (e.g. petroleum fractions), chlorinated aliphatic hydrocarbons (e.g. methylene chloride, etc.), alcohols (e.g. methanol, ethanol, propanol, butanol, etc.), amines (e.g. ethanolamine, etc.), ethers, ether-alcohols (e.g. glycol monomethyl ether, etc.), amides (e.g. dimethyl formamide, etc.), sulfoxides (e.g. dimethyl sulfoxide, etc.), ketones (e.g. acetone, etc.), and/or water; as well as inert dispersible finely divided solid carriers, such as ground natural minerals (e.g. kaolins, clays, alumina, silica, chalk, i.e. calcium carbonate, talc, attapulgite, montmorillonite, kieselguhr, etc.) and ground synthetic minerals (e.g. highly dispersed silicic acid, silicates, e.g. alkali silicates, etc.); whereas the following may be chiefly considered for use as conventional carrier vehicle assistants, e.g. surface-active agents, for this purpose: emulsifying agents, such as non-ionic and/or anionic emulsifying agents (e.g. polyethylene oxide esters of fatty acids, polyethylene oxide ethers of fatty alcohols, alkyl sulfonates, aryl sulfonates, etc., and especially alkyl arylpolyglycol ethers, magnesium stearate, sodium oleate, etc); and/or dispersing agents, such as lignin, sulfite waste liquors, methyl cellulose, etc.

Such active compounds may be employed alone or in the form of mixtures with one another and/or with such solid and/or liquid dispersible carrier vehicles and/or with other known compatible active agents, especially plant protection agents, such as other acaricides;insecticides, fungicides, bactericides and nematodices, or rodenticides, herbicides, fertilizers, growth-regulating agents, etc., if desired, or in the form of particular dosage preparations for specific application made therefrom, such as solutions, emulsions, suspensions, powders, pastes, and granules which are thus ready for use.

As concerns commercially marketed preparations, these generally contemplate carrier composition mixtures in which the active compound is present in an amount substantially between about 0.l95% by weight, and preferably 0.5-% by weight, of the mixture, whereas carrier composition mixtures suitable for direct application or field application generally contemplate those in which the active compound is present in an amount substantially between about 0.000l-l0%, preferably 0.014%, by weight of the mixture. Thus, the present invention contemplates over-all compositions which comprise mixtures of a conventional dispersible carrier vehicle such as (1) a dispersible inert finely divided carrier solid, and/or (2) a dispersible carrier liquid such as an inert organic solvent and/or water preferably including a surface-active effective amount of a carrier vehicle assistant, e.g. a surface-active agent, such as an emulsifying agent and/or a dispersing agent, and an amount of the active compound which is effective for the purpose in question and which is generally between about 0.0001- and preferably 0.01-95 by weight of the mixture.

The active compounds can also be used in accordance with the well known ultra-loW-volurne process with good success, i.e. by applying such compound if normally a liquid, or by applying a liquid composition containing the same, via very effective atomizing equipment, in finely divided form, e.g. average particle diameter of from 50- microns, or even less, i.e. mist form, for example by airplane crop spraying techniques. Only up to at most about a few liters/ hectare are needed, and often amounts only up to about 15 to 1000 g./hectare, preferably 40 to 600 g./ hectare, are sufficient. in this process it is possible to use highly concentrated liquid compositions with said liquid carrier vehicles containing from about 20 to about 95% by weight of the active compound or even the 100% active substance alone, e.g. about 20100% by weight of the active compound.

Furthermore, the present invention contemplates methods of selectively killing, combating or controlling pests, e.g. insects, acarids, nematodes, fungi and molluscs and more particularly methods of combating at least one of insects, acarids and nematodes, which comprises applying to at least one of correspondingly (a) such insects, (b) such acarids, (c) such nematodes, (d) such fungi, (e) such molluscs, and (f) the corresponding habitat thereof, i.e. the locus to be protected, e.g. to a growing crop, to an area where a crop is to be grown or to a domestic animal, a correspondingly combative or toxic amount, i.e. an insecticidally, acaricidally, nematocidally, fungicidally or molluscicidally effective amount of the particular active compound of the invention alone or together with a carrier vehicle as noted above. The instant formulations or compositions are applied in the usual manner, for instance by spraying, atomizing, vaporizing, scattering, dusting,

7 Watering, squirting, sprinkling, pouring, fumigating, and the like.

It will be realized, of course, that the concentration of the particular active compound utilized in admixture with the carrier vehicle will depend upon the intended application. Therefore, in special cases it is possible to go above or below the aforementioned concentration ranges.

The unexpected superiority and outstanding activity of the particular new compounds of the present invention are illustrated, without limitation, by the following examples:

EXAMPLE 1 To 15 g. of 2-hydroxy-7-methyl-pyrazolo(1,5-a)pyrimidine dissolved or suspended in 100 ml. of dimethyl formamide there are added 11 g. of triethylarnine and 18 g. of O-ethylethanethionophosphonic acid ester chloride. After 3 hours of stirring, the mixture is poured into water, taken up with methylene chloride, washed, dried and slight distilled. The yield is 22 g. (77% of theory), the refractive index is n =1.5670.

Calculated for C H O N SP (molecular weight 285): S, 11.2%. Found: S, 11.8%.

EXAMPLES 2-8 In manner analogous to that of Example 1, the following compounds can be prepared:

TABLEContinued Physical pl'ODGI'LlCS (refractive Compound index or M.P.)

(e) sec.-C4HO\fi M.P., 4-1-16 C.

l u 3 N 10 N llgcxJ (7) SEC-C(HIO fi nn i mi HaC (8) 1CaII1O\fi M.P., 60-62 C.

7i CZHS N I N sC I The starting material for Examples 1-8 can be prepared as follows:

N H30 I (I115) Into a solution of 40 g. of S-aminopyrazolone and 108 g. of acetoacetaldehydedimethylacetal in 300 ml. of dry ethanol there is introduced a vigorous stream of hydrogen chloride until the ending of precipitation. The precipitate is then filtered off with suction, triturated with a 2 N solution of sodium hydroxide, again filtered off with suction, and dried.

The yield is 25 g. (42% of theory), the melting point 209 C.

Calculated for CqH7ON3 (molecular weight 149): N, 28.2%. Found: N, 28.1%.

pyrimidine are dissolved in 300 ml. of acetonitrile and stirred for 3 hours at 50 to C. with 45 g. of potassium carbonate and 57 g. of 0,0-diethylthionophosphoric acid ester chloride. The mixture is then poured into water,

taken up with benzene, washed, dried and slightly distilled.

The yield is 47 g. (47% of theory), m.p. 54 C. For C H O N ClSP (molecular weight 336)Calculated: N, 12.5; Cl, 10.6; S, 9.5; P, 9.2%. Found N, 11.9; CI, 10.5;

9 EXAMPLES 10-12 In manner analogous to that of Example 9, the following compounds can be prepared:

The starting material required for Examples 9-12 is obtainable as follows:

75 g. of 2-hydroxy-7-methyl-pyrazolo(l,5-a)pyrimidine are dissolved in 1600 ml. of glacial acetic acid, and 38 g. of chlorine are introduced into the solution at 70 C. After stirring for 30 minutes at room temperature, 40 g.

of sodium hydroxide, dissolved in 100 ml. of water, are

added. The mixture is then heated to 90 C., cooled, the precipitate is filtered ofi with suction, washed with ether, and dried on clay.

Yield: 62 g. (67% of the theory).

EXAMPLE 13 me (1a) 46 g. of 2-hydroxy-3-bromo-7-methyl-pyrazolo(1,5-a) pyrimidine, suspended or dissolved in 200 ml. of acetonitrile, are stirred overnight with 22 g. of triethylamine and 33 g. of 0,0-di-ethylthionophosphoric acid ester chlride. The mixture is then poured into water, taken up with benzene, washed, dried and slightly distilled.

' The product melts at 72 to 74 C. The yield is 42 g. (55% of theory).

Calculated for C H 0 N BrSP (molecular weight 380): N, 11.1; S, 8.4; P, 8.2%. Found: N, 11.0; S, 8.3; P, 8.3%.

EXAMPLES 14-18 In manner analogous to that of Example 13, the follovving compounds can be prepared:

Melting point Compound (CzHaO)2P-O" Br N Ii I N Hie-d /P-O- Br 02H! N N HQCU seo.-C4HaO S -118 i 0 Br |l CHI N N ll (17). 1C H O S P-O Br 7 ll CH: N

J N H3O \J 1s s 92 The starting material for Examples 13-18 can be obtained as follows:

48 g. of bromine are added to 45 g. of 2-hydroxy-7- methyl-pyrazolo(1,S-a)pyrimidine in 1200 ml. of glacial acetic acid. After stirring for 20 minutes at room temperature, 24 g. of sodium hydroxide, dissolved in 60 ml. of water, are added. The mixture is then heated to 100 C., cooled, the precipitate is filtered off with suction, washed with ether, and dried on clay.

The yield is 40 g. (59% of theory), the melting point 186 C. (with decomposition).

Calculated for C H ON Br (molecular weight 228): N, 18.4; Br, 35.1%. Found: N, 18.7; Br, 35.2%.

The invention will be further illustrated in the following comparative examples and tables.

EXAMPLE 19 Pluetta test Solvent: 3 parts by weight acetone Emulsifier: 1 part by weight alkylarylpolyglycol ether To produce a suitable preparation of active compound,

12 After the specified periods of time, the degree of destruction is determined as a percentage: 100% means that all the caterpillars are killed whereas that none of the caterpillars are killed.

The active compounds, the concentrations of the active compounds, the evaluation times and the results can be seen from Table 1.

TABLE 1. PLUTELLA TEST) Concen- Degree oi tration destruction of active in percent compound after Active compounds in percent x8 days (A) CH: 0.1 100 0. 01 100 0.001 t l (CzH)zP-O CH1 (known) (B) CH: O. 1 100 I 0. 01 100 0.001 0 CzHs\ i I PO CH; N CzHsO (known) (4) CH: 0.1 100 s2 N-N (CH O) P-O (18) CH; 0.1 100 0. 01 100 A 0. 001 i (CHIO)2PO N/ (3) CH1 0. 1 100 0.01 100 0.001 100 i M (C H O):PO

z s N/ (9) CH: 0. 1 100 0.01 100 0.001 100 i U (C H O) PO (13) CH: 0. l 100 0.01 100 0.001 t I (C:H50)2P-O N (2) C H: 0. l 0.01 100 0.001 100 W (C H 0) PO TABLE 1-Continued Concen- Degree of tration destruction of active in percent compound after Active compounds in percent 3 days (14) CH: 0. 1 100 N 0 (fl) U (CzHaOhP-O l Br (1) CH; 0. 1 100 0. 01 100 0. 001 100 CzHs S N CzHsO (11) CH; 0. 1 100 o b i N 0 CHI 5 i 0 N 2310 A:

1 (15) CH: 0. 1 100 0. 01 100 0. 001 100 02115 S N CzHaO r (5) CH: 0. 1 100 I 0. 01 100 0. 001 100 CH! S i o N V (CHa)zCHO (17) CH; 0. 1 100 I 0. 01 100 0. 001 100 CH: S

O N (CHQzCH-O l Br (s) CE; 0.1 100 1 0. 01 100 r V 0. 001 100 01H! 8 \g 4 N (CHx):CH-O (6) CH: O. 1 100 l 0. 01 100 0. 001 100 CH: 8 CH l 0 CH-O 02H:

(16) CH1 0. l 100 A :23 N CH: S \ll CH; P-O N CH-O I Br 01H:

(7) CH; 0. 1 100 l a 01 100 0. 001 70 02H; 8

CH-O

15 16 EXAMPLE 2O Cabbage plants (Brassica oleracea) which have been heavily infested with peach aphids (Myzus persicae) are Myzus test (Contact acnon) sprayed with the preparation of the active compound until dripping wet.

After the specified periods of time, the degree of destruction is determined as a percentage: 100% means that Solvent: 3 parts by weight acetone Emulsifier: 1 part by weight alkylarylpolyglycol ether 5 To produce a suitable preparation of active compound, all the aphids are killed whereas 0% means that none of 1 part by weight of the active compound is mixed with the aphids are killed. the stated amount of solvent containing the stated amount The active compounds, the concentrations of the active of emulsifier and the concentrate is diluted with water to compounds, the evaluation times and the results can be the desired concentration. seen from the following Table 2.

TABLE 2.(MYZUS TEST) Concen- Degree of tration destruction of active in percent compound after Active compounds in percent 1 day (C) CH; 0. 1 98 i 0. 01 0. 001 0 N I 2 s )2 OH;

(known) (D) CH; 0. 1 l 0. 01 20 0. 001 0 N i ll (CzHs0)zP-O N CH;

l Br

(known) (E) CH; 0. 1 10 o I 0. 01 9 0. 001 0 l (CzHsO)2 CHI (known) (F) CH1 0. l 100 1 at: i l 2H5Q)zPO CH;

(known) t NN i (CH:O)zP-0 N 1 CH 0. 1 100 8) a 0 01 100 I N N/\ 0. 001 100 3 CH 0. 1 100 a 0.01 100 0.001 N.

19 201 TABLE 2Continued Concen- Degree of V V V tration destruction of active in percent compounds after Active compounds in percent 1 day (8) CE; 0.1 100 I 0.01 100 0.001 98 NN it 1 iP-o N (CHQzCH-O (6) CH; 0.1 100 I 0.01 99 v 0.001 80 NN CH3 S OH O N /CH0 C2 (7) CE; 0.1 100 0.01 100 0.001 98 Ki CE; /PO N,

/CH-O 02H EXAMPLE 21 preparation of the active compound until dripping wet.

Tetranychus test Solvent: 3 parts by weight acetone Emulsifier: 1 part by weight alkylarylpolyglycol ether 35 of emulsifier and the concentrate so obtained is diluted 40 with water to the desired concentration. Bean plants (Phaseolus vulgaris), which'have a height of approximately 10-30 cm., are sprayed with the These bean plants are heavily infested with spider mites (Tetranychus urticae) in all stages of development.

After the specified periods of time, the effectiveness of the preparation of active compound is determined by counting the dead mites. The degree of destruction thus obtainedis expressed as a percentage: 100% means that all the spider mites are killed whereas 0% 'means that none of the spider mites are'killed V p I The active compounds, theconcentrations of the active compounds, the evaluation timcs'and the results can be seen from the following Table 3.

TABLE 3.(TETRANYCHUS TEST) (known) 21 TABLE 3Continued Concen- Degree 0! tration destruction of active in percent compound after Active compounds in percent 2 days (F) (IJH; 0.1 0

3 I (CaH;O)1PO N, CH:

(known) (B) "2:: CH; 0:1 0

P-O OH:

(G) CH: 0:1 0

O CH; N C;H;O

( now (10)-.:.T.:::= CH; 0.1 100 0.01 100 i (OHaO)A?-O (C;H;0):r O

B {l 1 1 N/ (13) ..-::T.' CH: 0. 1 100 I 0.01 98 fi (C:H50):P-0 N (3) CH: 0. 1 100 l 0.01 90 "i (C;H50):P0 N

N u (CzHgOhP-O N,

23 24 TABLE 3-Continued Coneen- Degree of tratlon destruction of active in percent compound after Active compounds in percent 2 days N N u (C H O) P-O (1)-": CH: 0.1 100 l o. 01 70 P-O N, CiHaO (11) CH: 0.1 100 I 0.01 100 l 0 N CzHaO l O A, N

CzHsO (5).;;...:.:;r.' CH1 0. 1 100 I 0.01 98 CH: S

l' o N (CHa):CH-O

EXAMPLE 22 LDmo tCSt Test insects: Sitophilus granan'us Solvent: acetone there is a filter paper with a diameter of about 9.5 cm. The Petri dish remains uncovered until the solvent has completely evaporated. The arj'nount of active compound per square meter of filter paper varies with the concentration of the solution of active compound used. 10 test insects are then placed in the Petri dish and it is covered with a glass lid. a

The condition of the test insectsis observed 3 days after the commencementof the experiments. The destruction is-deter'rnined as a percentage. 5

The active compounds, the concentrations of the active compounds, the test insects and the results can be seen from the following Table 4.

TABLE 4.Continued Concentration of active com- Destrucpound tion in Active compound in percent percent (12) CH; 02 100 0.02 100 0.002 N-N I? OP(OC:H):

EXAMPLE 23 TABLE 5Continued L'I test for Diptera Test insects: A'des aegypti 5 83:; Solvent: acetone Active compounds in percent LI 2 parts by weight of active compound are dissolved in 1000 parts by volume of solvent. The solution so obtained is diluted with further solvent to the desired lower 1 S concentrations. I II 2.5 ml. of the solution of active compound are'pipetted H3O O-HOUZHS) into a Petri dish. On the bottom of the Petri dish there A is a filter paper with a diameter of about 9.5 cm. The Petri dish remains uncovered until the solvent has com- (known) pletely evaporated. The amount of active compound per (mun CH: M square meter of filter paper varies with the concentration I 0.02 of the solution of active compound used. About 25 test insects are then placed in the Petri dish and it is covered I I i with a glass lid. l O P(OCH3),

The condition of the test insects is periodically ob- V served. The time which is necessary for a 100% destruction is determined.

The tests insects, the active compounds, the concentra- (9) CH3 i M trons of the active compounds and the periods of time ,1 M2 at which there is a 100% destruction can be seen from 40 v the following Table 5. I i

OP(OC2 s):I TABLE 5.(L'I TEST FOR DIPTERA) N I Concen- C] ftraiiion 0 80 V8 r c d 2) cm a 0.2 60 Active compounds l i p e nt L'lm I 180 (E). on; 0.2 120' -F 0 ll f\, O Vo-Pwcmm ll HzC \NU0P(0C1H5)I (3) a CH: W A" 0.2 I 0.02 180' (known) 55 -i S II '7 m 311 0.2 3h={)()% NMOP(OC2H5)2 5 CH 0.2 n 60 U I a 0.02 HaC \N 0P(0C2H:): N i I: T-

il} fi/ H! \N (known) 5 03H! CH3 M 3h=0% EXAMPLE 24 1 Critical concentration test/soil insects s F Test insect: Cabbagerootfiy maggots (Phorbza bras- H sicae) H3O OP (OC:Hs)2 N Solvent: 3 parts by weight acetone Emulsifier: 1 part by weight alkylarylpolyglycol ether (known) To produce a suitable preparation of active compound 7.3 1 part by weight of active compound is mixed with the 29 stated amount of sol-vent, the stated amount of emulsi fier is added and the concentrate is diluted with water to the desired concentration. The preparation of active compound is intimately mixed with soil. The concentration of the active compound in the preparation is of practically no importance; only the amount of active compound per unit volume of soil, which is given in p.p.m. (for example mg./ 1.), is decisive. The soil is filled into pots and the pots are left to stand at room temperature.

After 24 hours, the test animals are put into the treated soil and, a further 48 hours, the degree of effectiveness of the active compound is determined as a percentage by counting the dead and living test insects. The degree of destruction is 100% when all the test insects have been killed; it is when exactly as many test insects are still alive as in the case of the control.

The active compounds, the amounts applied and the results can be seen from the following Table 6.

TABLE 6.--(SOIL IN SECTICIDES/PHORBIA BRASSICAE MAGGOTS) Degree of destruction in percent with concentration of active compound in p.p.m. oi

Active compounds 20 5 2. 5

(13) CzHsO S 100 100 95 70 \II /P0 Br 21150 N N m I (15)-:::;:: CzHz\fi 100 100 /P0 Br czmo i l] (17).::: i OCsHr-i 100 100 92 CH3-P 0 Br N l N MU (7).::::- sec.-C4H4|O\fi 100 95 5O /PO Br 02 l N m l (8).:212'. i-C:H1O SI 100 50 /PO Br 02H: 11

N m l (12)-.-' C2Ha0\fi 100 100 100 70 v v Degreeofdestructionin 1 l q V V percent with concentration I 'of active compound in a- Y I i p.p.rn.0i

Active compounds 20' 1o. 5 2.5

\N O-P (O CzHr): 3 I

l Br

(known) IC).::. (EH: 0

HC O H OCH 3 \N P( z 5):

(known) EXAMPLE The concentration of the active compound in the prepara- Critical concentration test Test nematode: Meloidogyne sp. Solvent: 3 parts by weight acetone Emulsifier: 1 part by weight alkylarylpolyglycol ether tion is of practically no importance; only the amount of active compound per unit volume of soil, which is given in p.p.m., is decisive. The soil is filled into pots, lettuce is sown in and the pots are ketp at a greenhouse temperature of 27 C. After 4 weeks, the lettuce roots are examined for infestation with nematodes, and the degree of destruction of the active compound is determined as a percentage. The degree of effectiveness is when infestation is completely avoided; it is 0% when the infestation is exactly the same as in the case of the control plants in untreated soil which has been infested in the same manner.

The active compounds, the amounts applied and the results can be seen from the following Table 7.

TABLE 7.-(NEMATO CIDES/MELOIDO GYNE IN CO GNITA) Degree of destruction in percent with a concentration of active compound in TABLE 7Continued Degree of destruction in percent with a concentration of active compound in p.p.m. of

Active compounds 40 20 10 (9) CzHgO S 100 100 90 P-O -Cl CzHrO (C)- Grill: 0

u HsC \N 0-P(OC:H:):

(known) EXAMPLE 26 microplus (sensitive and resistant, respectively) are immersed for one minute in these preparation of active com- Tick test pound. After immersion of, in each case, female speci- Solvent: 35 parts by weight ethyleneglycolmonomethyl 30 ether Emulsifier: parts by weight nonylphenolypolycol ether To produce a suitable formulation, 3 parts by weight 35 Adult, gorged female ticks of the species Boophilus mens of the various tick species, they are transferred to Petri dishes, the bottom of which is covered with a correspondingly large filter disc.

After 10 days, the effectiveness of the preparation of active compound is determined by ascertaining the inhibition of egg deposition compared with untreated control ticks. The effect is expressed as a percentage, meaning that eggs ceased to be deposited, and 0% signifying that the ticks deposited eggs in normal amount.

The active compounds investigated, the concentrations tried, the parasites tested and the findings obtained can be seen from the following Table 8.

TABLE 8.(TICK TEST) Inhibition of egg deposition in Concenpercent-Beephilul tration microplu:

Biarra Active compounds strain ll (CHIC) zPO 100 O 0 TABLE 8-Continued lnhibitionpf egg deposition Concenpercent-Baophilux tration microplus of active com- Ridgepound land Blarra Active compounds in p.p.m. Strain stram (l2) 10,000 100 100 ll 1.000 100 50 (C:H;O):-P0ly-ICl J N J (13) S 10, 000 100 50 II 1,000 100 50 (C;H;0):P-Ol1TBr 100 50 0 N Hie-U (14) 0 10,000 100 50 g 1,000 50 50 (C1H0) 0] '*BI 02H; 5 10,000 100 100 \ll 1,000 100 1. Br CzH50 i N /\N mo l (10).:;;: 8 1g,% 53 m-omo-i -o-l B: '100 50 0 H0 l l (170.7522 1Ct 1 1:1, i -0--| B1- '100 0 Cr. ,J

s l cmo -i-o-li Br N MQ EXAMPLE 27 Test with parasitizing fly larvae Solvent: 35 parts by weight ethyleneglycolmonomethyl ether Emulsifier: 35 parts by weight nonylphenolpolyglycol ether To produce a suitable preparation of active compound,

plied to this horsefiesh. After 24 hours, the degree of The active compound tested, the concentration applied destruction is determined as a percentage. 100% means and the test results obtained can be seen from Table 9. that all, that no, larvae have been killed.

TABLE 9 (Lucilt'a cuprfna) Concentration Degree of of active destruccompound tion in Active compounds in p.p.m. percent (2) O 300 100 (C H O) l l 0 3g 8 z a 2- N l N J (3) S 300 100 ll 30 100 (CZII50)QP OH" 3 50 N 1G I (4) S 300 100 ll 30 50 :O): O-H N l N H;O I

(5) 11 0 S 300 100 T? CH: N

N Hie-U (6) sec.-C4H0 S 300 \{l 0 33 100 50 7! CH: N

(7) sec.-C4Hq0 S 300 50 l 0 "2 223 7! C311. N

N H; I

(8) 1CaH1O S 300 100 l 0 3 228 ll CzHa N (9) S 300 100 ll 30 100 (CzH;O)rP-O"-- Cl 3 50 N IF 

1. A METHOD OF COMBATING A PEST SELECTED FROM THE GROUP CONSISTING OF INSECT, ACARID, AND NEMATODE PEST WHICH COMPRISES APPLYING TO THE PESTS OR A HABITAT THEREOF AN INSECTICIDALLY, ACARICIDALLY, OR NEMATOCIDALLY EFFECTIVE AMOUNT OF AN O-PYRAZOLOPYRIMIDINE-(THIONO)-PHOSPHORIC (PHOSPHONIC) ACID ESTER OF THE FORMULA: 